Heterojunction oxide non-volatile memory device

ABSTRACT

A memory device includes a first metal layer and a first metal oxide layer coupled to the first metal layer. The memory device includes a second metal oxide layer coupled to the first metal oxide layer and a second metal layer coupled to the second metal oxide layer. The formation of the first metal oxide layer has a Gibbs free energy that is lower than the Gibbs free energy for the formation of the second metal oxide layer.

CROSS-REFERENCES TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.13/396,404 filed on Feb. 14, 2012, which claims priority to and is acontinuation of International Patent Application No. PCT/US2010/045667,filed on Aug. 16, 2010, which claims priority to U.S. Provisional PatentApplication No. 61/234,183, filed on Aug. 14, 2009. The content of allthese applications is incorporated by reference herein in its entiretyfor all purposes.

FIELD OF INVENTION

The present invention relates generally to memory devices, and moreparticularly to a memory device that includes hetero junction oxidematerial.

BACKGROUND

As Moore's Law has been predicting, the capacity of memory cells onsilicon for the past 15-20 years has effectively doubled each year.Moore's Law is that every year the amount of structures or gates on asilicon wafer will double, but the price will essentially stay the same.And in some cases, the price will even erode. As these memory cellscontinue to shrink, the technology is starting to reach a barrier knownas the quantum limit, that is, they are actually approaching molecularboundaries, so the cells cannot get any smaller.

Disk drives have been the dominant prime storage in terms of peakcapacity, because storing individual domains (magnetic transition sites)on the disk drives unlike semiconductor memory cells disk memory sitesdo not require connections to get in and out of those domains. Now, inrecently history, semiconductor resolutions apply feature geometrieswith 90 nanometer feature resolutions progressing to 45 and 25 nanometerfeature size sizes, with these feature capabilities, the memory cellsize and chip capacity equation changes, furthermore, certainsemiconductor memory technologies have applied a principal of geometricredundancy, where a multiple of data bits may be stored in a singlecell. This property of a memory cell to support a multiple of values issometimes referred to as its dynamic range. To date the for memory cellshave abilities to support a dynamic range anywhere between 1 and 4 bits,gives you multiples of storage per memory cell. These combinedproperties of semiconductors, have increased capacities and costs to nowdirectly compete with disk drives.

Another issue associated with semiconductor memory manufacturing hasbeen the substantial costs of the semiconductor foundries which can runup to more than a billion dollars to establish with amortizing expensesinflating the unit cost of memory chips. In recent history thisrepresented price barriers compared with cost per capacity of a diskdrive file. Now, with advances in foundry resolutions enabling smallercell sizes and the geometric redundancy of multiple bit-level per memorycell semiconductor memory is actually cheaper per unit cost, andsubstantially more rugged in terms of high G forces than memory files ona disk drive.

In Flash memories, there have been improvements in the Moore's Laweffect but that has become a diminishing proposition because as thecells started getting smaller and smaller, write cycle limitations andability to support dynamic ranges are diminished.

So basically, as characterized in recent press review, Flash memory hashit the proverbial wall in increasing data capacity per unit cost, asthe quantum limit is approached.

But another issue with Flash memory is its limitations in write speeds.In order to compete with disk drive performance, the memory cells wordstructure is configured to switch in parallel. Another issue is thenumber of write cycle limitations the cell will tolerate before itpermanently fails. Prior to the substantial reduction in cell size, itwas approximately in the range of one million, however, as the foundryfeature size resolutions reduced in size, rewrite cycle diminished toapproximately 100,000 write cycles. For most non-prime storageapplications that may be practical. However, for SRAM and DRAMapplications where you're actually exchanging data at substantialrepetition rates, several times per microsecond.

Accordingly, what is desired is a memory system and method whichovercomes the above-identified problems. The system and method should beeasily implemented, cost effective and adaptable to existing storageapplications. The present invention addresses such a need.

SUMMARY

A memory device is disclosed. The memory device comprises a first metallayer and a first metal oxide layer coupled to the first metal layer.The memory device includes a second metal oxide layer coupled to thefirst metal oxide layer and a second metal layer coupled to the secondmetal oxide layer. The formation of the first metal oxide layer has aGibbs free energy that is lower than the Gibbs free energy for theformation of the second metal oxide layer.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1A illustrates a memory device in accordance with an embodiment.

FIG. 1B illustrates a memory device according to another embodiment ofthe present invention.

FIG. 2 is a graph showing resistance versus the Gibbs free energy forvarious metals.

FIG. 3 illustrates a set of transmission electron micrographs (TEM's)that show the cross sections of formation of (or no formation of) metaloxide at the junction of two types of interfaces according to anembodiment of the present invention.

FIG. 4 illustrates the classification of PCMO devices in accordance withembodiments of the present invention.

FIG. 5 is a graph showing hysteresis loops for two types of memorydevices according to an embodiment of the present invention.

FIG. 6 illustrates the characteristics of the PCMO devices of FIG. 5.

FIG. 7A illustrates providing the metal 2 on a silicon surface.

FIG. 7B illustrates sputtering metal 2 oxide onto the metal 2 surface.

FIG. 7C illustrates metal oxide 1 forming spontaneously by providingmetal 1 of the right energy level on the metal 2 oxide.

FIG. 7C′ illustrates the metal oxide 1 sputtered on to the metal oxide 2surface, and an inert metal is provided on top of the metal 2 oxide.

FIG. 8 illustrates the operation of a switchable resistor that has aclockwise hysteresis of current versus voltage and a switchable resistorthat has a counter clockwise hysteresis of current to voltage.

FIG. 9 is a diagram of a back to back switching resistor in accordancewith an embodiment.

FIG. 10 is a diagram of the operation a tri-state back-to-back switchingresistor device.

FIG. 11 illustrates first method for addressing the tri-states of theback to back switching device of FIG. 10.

FIG. 12 is a diagram illustrating identifying the 00 state vs. 01, 10state (nondestructive read).

FIG. 13 is a diagram illustrating identifying a 10 state vs. 01 state(destructive read, need to reinstall the state after read).

FIG. 14 illustrates addressing single cell of an array in accordancewith an embodiment.

FIG. 15 illustrates creating asymmetry in the device to eliminate theneed for resetting the device.

DETAILED DESCRIPTION

The present invention relates generally to memory devices, and moreparticularly to a memory device that includes a heterojunction oxidematerial. The following description is presented to enable one ofordinary skill in the art to make and use the invention and is providedin the context of a patent application and its requirements. Variousmodifications to the preferred embodiments and the generic principlesand features described herein will be readily apparent to those skilledin the art. Thus, the present invention is not intended to be limited tothe embodiments shown, but is to be accorded the widest scope consistentwith the principles and features described herein.

The present invention is directed to a memory device. The memory devicecan be utilized in a variety of applications from a free standingnonvolatile memory to an embedded device in a variety of applications.These applications include but are not limited to embedded memory usedin a wide range of SOC (system on chip), switches in programmable orconfigurable ASIC, solid state drive used in computers and servers,memory sticks used in mobile electronics like camera, cell phone, iPod®etc. The memory device comprises a first metal layer and a first metaloxide layer coupled to the first metal layer. The memory device includesa second metal oxide layer coupled to the first metal oxide layer and asecond metal layer coupled to the second metal oxide layer. These metaland metal oxide layers can be of a variety of types and their use willbe within the spirit and scope of the present invention. Moreparticularly, many of the embodiments disclosed herein will include PCMOas one of the metal oxide layers. It is well understood by one ofordinary skill in the art that the present invention should not belimited to this metal oxide layer or any other layer disclosed herein.The key element is that the formation of the first metal oxide layer hasa Gibbs free energy that is lower than the Gibbs free energy for theformation of the second metal oxide layer.

FIG. 1A is an illustration of a memory device 10 which includes aPlatinum (Pt) bottom electrode 16, which in turn is coupled to aPraseodymium Calcium Manganese Oxide (PCMO) layer 14 which in turn iscoupled to a top electrode 12 which is made of a metal. If a Gibbs freeenergy for the formation of oxidation of the top electrode 12 is less(more negative) than a Gibbs free energy for the formation of oxidationof the PCMO layer 14, the top electrode metal 12 will spontaneously forma thin metal oxide 18 at the interface as shown in FIG. 1B. The firstmetal oxide layer is preferably thinner than the second oxide layer. Inan embodiment, the second metal oxide layer (in this case PCMO) istwenty to fifty times thicker than the first metal oxide layer. Forexample, the thickness of the first metal oxide layer is in the range often to fifty angstroms, and the thickness of the PCMO is 500 to 1000angstroms.

Referring now to FIG. 2, what is shown is a graph showing resistanceversus the Gibbs free energy free energy for various top metals coupledto PCMO, which is in turn coupled to a Pt bottom electrode. As is seen,elements such as gold, silver, and platinum, which have a higheroxidation Gibbs free energy than PCMO, will not spontaneously form oxideat the contact with the PCMO. However aluminum, titanium, and tantalum,have a lower oxidation Gibbs free energy (more negative) than PCMO whichallows for a spontaneously forming metal oxide upon contact therebetween. FIG. 3 is a set of transmission electron micrographs that showthe cross sections of formation of (or no formation of) metal oxide atof these two types of interfaces. As is seen in electron micrograph 102which shows an interface between Platinum and PCMO there is no formationof a metal oxide. Electron micrographs 104-106 all illustrate theformation of a metal oxide when aluminum, titanium and tantalumrespectively are interfaced with PCMO.

FIG. 4 shows a method to classify various as-made “metal-PCMO-metal”devices into two types based on the relative value of the oxidationGibbs free energy of the metal with relative to the oxidation Gibbs freeenergy of PCMO. For Type-I devices, both the top and bottom metalelectrode have a higher oxidation Gibbs free energy than the oxidationfree energy of PCMO. The device structure is metal-PCMO-metal orM/PCMO/M. For Type-II devices, one of the metal electrodes (topelectrode) has a lower oxidation Gibbs free energy than the Gibbs freeenergy of PCMO. Due the spontaneous formation of the metal oxide at thecontact with PCMO, the true device structure becomes metal-metaloxide-PCMO-metal, or M/MO/PCMO/M. Thus, a Type-II device is a heterojunction metal oxide device. The above rule of using the relative valuesof the oxidation free energy with respect to a base metal-oxide materialcan be generalized to any metal oxide. For example, Al, Ta and Ti canform Type-II device with a Tungsten Oxide which is coupled to Pt, Au orAg as indicated in FIG. 2.

FIG. 5 shows that the above Type-I and Type-II devices yield differentcurrent-voltage (I-V) hysteresis curves. A Type-I device (202 a, 202 band 202 c) yields a counter clock wise (CCW) hysteresis loop, while aType-II device (204 a, 204 b and 204 c) yields a clock wise hysteresisloop. Furthermore, the hysteresis loop of the Type-II device isconsiderably larger than the hysteresis loop of Type-I devices. The CCWloop and CW loop will be swapped if the polarity of the bias isinterchanged. These unique I-V characteristics can be utilized forvarious applications.

The different hysteresis loops imply that both PCMO and metal-oxide areswitchable resistors and a voltage with the correct polarity andamplitude can cause the resistor to switch from a low resistive state(LRS) to a high resistive state (HRS) (RESET), or from a HRS to a LRS(SET). Typically, the lower oxidation Gibbs free energy will result in amore stable oxide structure which has a much higher resistance in HRSthan the resistance of PCMO in HRS. The metal oxide layer is muchthinner than PCMO and its resistance at LRS is comparable to theresistance of PCMO at HRS. This feature is quite important. When themetal oxide is in HRS, most of the voltage applied to the Type-II devicewill drop across the metal oxide and hence create a high internal fieldthat causes the switching from HRS to LRS (SET). On the other hand, whenthe metal oxide is in LRS, the voltage apply to the Type-II device willbe shared in metal-oxide and in PCMO and hence allow field inducedoxygen ion migrations in these metal oxide layers.

These concepts are used to advantage to provide a heterojunctionnonvolatile memory device which can retain data over a significantperiod of time. FIG. 6 illustrates the characteristics of each of thesetypes of devices. As is seen although both types can be utilized asmemory devices the Type-II device is more effective and has bettercharacteristics. The key element is that the formation of the firstmetal oxide layer has a Gibbs free energy that is lower than the Gibbsfree energy for the formation of the second metal oxide layer. In sodoing the two metal oxide layers provide a heterojunction that allowsfor the continual setting and resting of the device.

FIGS. 7A-7C′ illustrate the process of producing such a device. FIG. 7Aillustrates providing the metal 2 on a silicon surface. FIG. 7Billustrates sputtering metal oxide 2 onto the metal 2 surface. The nextstep is one of two alternative processes. Firstly, as seen in FIG. 7C,metal oxide 1 is formed spontaneously by providing metal 1 on the metaloxide 2, where the metal oxide 1 has a lower oxidation free energy thanthat of metal oxide 2 so that metal oxide 1 can be form spontaneouslybetween metal 1 and metal oxide 2. As an alternative as shown in FIG.7C′ the metal oxide 1 is sputtered on to the metal oxide 2 surface, andan inert metal is provided on top of the metal 1 oxide. Through the useof this system, a heterojunction oxide non-memory device can be providedthat has characteristics that are significantly better than existingdevices.

The heterojunction switchable resistor can be used to construct highdensity memory array. Since it is a bipolar device, in general, itrequires a transistor circuit to address (select, set, reset and read)individual device as in many prior arts. In a system in accordance withthe present invention, back to back resistive devices are utilized toeliminate the need of the transistor circuit. This type of memory systemwill use less power, and fewer processing steps than conventional memorysystems. More importantly it allows an easy way for form a multi stackmemory cell that further improves the cell density per unit source area.

FIG. 8 illustrates a switchable resistor 302 that has an idealizedclockwise hysteresis of current versus voltage (I-V) 306 and aswitchable resistor 304 that has an idealized counter clockwise I-Vhysteresis 308. CW and CCW switching resistors 302 and 304 can beType-II and Type-I device shown in FIG. 5 by the choice of the top metalelectrode. They can also be constructed by using the same type devicewith top and bottom electrode reversed. In the FIG. 8 we use theidealized I-V characteristics to illustrate an embodiment of a switchingresistor device. It is clear to hysteresis one of ordinary skill in theart that a real device will have I-V curve that differs from the idealones used here. However, the principle remains valid even with a realdevice I-V.

FIG. 9 is a diagram of a back to back switching device 320 in accordancewith an embodiment, and the I-V characteristics of such a combineddevice. These two resistors 302′ and 304′ have identical idealized I-Vcharacteristics but with opposite polarities. The I-V characteristic isdue to the fact that when one resistor is switching from HRS to LRS, theother resistor is switching from LRS to HRS. By using a switchingvoltage between the threshold voltages Va and Vb (with in positive sideor negative side), both resistors 302 and 304 can be switched into LRS.

FIG. 10 shows that back-to-back switching device 320′ can give rise to atri-state. When either resistor 302′ or 304′ is in HRS, the device 320is in HRS. So there are two HRS, 01 or 10 state. When both resistors arein LRS, the device is in LRS, or 00 state. The table 408 in FIG. 11illustrates a method for addressing the tri-states of the back to backswitching device 320 of FIG. 10. In general, 00 state can be set to 01or 10 state and vice versa. FIG. 12 is a diagram illustrating a methodto identify the 00 state 502 vs. 01, 10 state 504. Here the read voltageis within the two lower threshold voltage (Va−<V<Va+), therefore thedevice will remain in the original state. This is a nondestructive read.

The nondestructive read can only differentiate the 00 state (LRS) fromeither the 01 or 10 state (HRS state). To further differentiate 01 vs.10 state, the polarity of the switching voltage (Vb−<V<Va− or Va+<V<Vb+)needs to be tested that cause the switching of HRS resistor to LRS.Since this is a destructive read, an additional pulse is needed to resetthe device to the initial state before the destructive read. FIG. 13 isa diagram illustrating a method for identifying a 10 state vs. a 01state. It is readily apparent to one of ordinary skill in the art thatmany other voltage pulses and sequences can be generated to read thetri-state.

The addressable and readable tri-state of a back-to-back switchingresistor device can be used to create a memory array that avoid the needof an active transistor circuit to perform the select and set/reset andread. For example, since 01 and 10 states are two addressable anddistinguishable HRS, they can be assigned to be the 0 or 1 state of amemory cell. Since both 0 and 1 state have high resistance, the systemshould have very low leakage current. A positive or negative voltagegreater than Vb+ or smaller than Vb− can set the device to 1 or rest thedevice to 0 state as shown in the table for FIG. 11. For read operation,perform a test pulse to set the cell to 00 state and from the polarityof the bias to extract the 10 or 01 state. Note that the original stateneeds to be reinstalled after the read operation.

In order to address a particular memory cell, proper voltage on the readand write line are required so that the state of other cells in thememory array is not affected. FIG. 14 illustrates a diagram of biasingpatterns that can fulfill this requirement when addressing single cellof an array in accordance with an embodiment.

The above discussions are based on two identical heterojunction oxideresistors. If the HRS states of the two switching resistors 702 and 704have sizable differences as illustrated in FIG. 15, than it is possibleto perform a nondestructive read of a back-to-back resistor device. Byso doing, we can eliminate the need for resetting the device after theread.

Although the present invention has been described in accordance with theembodiments shown, one of ordinary skill in the art will readilyrecognize that there could be variations to the embodiments and thosevariations would be within the spirit and scope of the presentinvention. Accordingly, many modifications may be made by one ofordinary skill in the art without departing from the spirit and scope ofthe appended claims.

1. A device comprising: a substrate having an upper surface and anopposing lower surface; a first metal layer coupled to the uppersurface; a Praseodymium Calcium Manganese Oxide (PCMO) layer coupled tothe first metal layer; a metal oxide layer coupled to the PCMO layer;and a second metal layer coupled to the metal oxide layer, wherein afirst Gibbs free energy for the metal oxide layer is lower than a secondGibbs free energy for the PCMO layer, wherein the PCMO layer ischaracterized by a first state having a first resistance and a secondstate having a second resistance and the metal oxide layer ischaracterized by a third state having a third resistance state and afourth state having a fourth resistance, and wherein the firstresistance is higher than the second resistance and the third resistanceis higher than the fourth resistance.
 2. The device of claim 1 whereinthe substrate comprises silicon.
 3. The device of claim 1 wherein thefirst metal layer comprises one of: aluminum, titanium, tantalum, gold,silver, or platinum.
 4. The device of claim 1 wherein the metal oxidelayer comprises one of: TiO₂, Ta₂O₅, NiO, WO₃, or Al₂O₃.
 5. The deviceof claim 1 wherein the second metal layer comprises one of: aluminum,titanium, tantalum, gold, silver, or platinum.
 6. The device of claim 1wherein the first metal layer comprise an inert metal.
 7. The device ofclaim 1 wherein the PCMO layer is characterized by a first thickness andthe metal oxide layer is characterized by a second thickness, whereinthe first thickness is twenty to fifty times more than the secondthickness.
 8. The device of claim 7 wherein the second thickness is inthe range of 10 to 50 angstroms.
 9. The device of claim 1 wherein thePCMO layer is characterized by a first thickness and the metal oxidelayer is characterized by a second thickness, and wherein the firstthickness is three to five times more than the second thickness.
 10. Adevice comprising: a silicon substrate having an upper surface and alower surface; a platinum layer overlying and coupled to the uppersurface; a Praseodymium Calcium Manganese Oxide (PCMO) layer overlyingand coupled to the platinum layer; an aluminum oxide layer coupled toand overlying the PCMO layer; and an aluminum layer overlying andcoupled to the aluminum oxide layer, wherein a first Gibbs free energyfor the aluminum oxide layer is lower than a second Gibbs free energyfor the PCMO layer.
 11. The device of claim 10 wherein the first Gibbsfree energy is about two to three times lower than the second Gibbs freeenergy.
 12. The device of claim 10 wherein the PCMO layer ischaracterized by a first thickness and the aluminum oxide layer ischaracterized by a second thickness, and wherein the first thickness isthree to five times more than the second thickness.
 13. The device ofclaim 10 wherein the PCMO layer is characterized by a first thicknessand the aluminum oxide layer is characterized by a second thickness,wherein the first thickness is twenty to fifty times more than thesecond thickness.
 14. The device of claim 13 wherein the first thicknessis in the range of 500 to 1000 angstroms.
 15. The device of claim 13wherein the second thickness is in the range of 10 to 50 angstroms. 16.A memory device comprising: a first metal layer; a Praseodymium CalciumManganese Oxide (PCMO) layer overlying and coupled to the first metallayer; a metal oxide layer coupled to the PCMO layer; and a second metallayer coupled to the metal oxide layer, wherein a first Gibbs freeenergy for the PCMO layer is higher than a second Gibbs free energy forthe metal oxide layer, wherein the thickness of the PCMO layer is twentyto fifty times more than a second thickness of the metal oxide layer.17. The memory device of claim 16 wherein the PCMO layer ischaracterized by a first state having a first resistance and a secondstate having a second resistance and the metal oxide layer ischaracterized by a third state having a third resistance state and afourth state having a fourth resistance, and wherein the firstresistance is higher than the second resistance and the third resistanceis higher than the fourth resistance.
 18. The memory device of claim 17wherein first resistance is similar in value to the fourth resistance.19. An electronic device comprising: a memory device, wherein the memorydevice comprises: a substrate having an upper surface and an opposinglower surface; a first metal layer coupled to the upper surface; aPraseodymium Calcium Manganese Oxide (PCMO) layer coupled to the firstmetal layer; a metal oxide layer coupled to the PCMO layer; and a secondmetal layer coupled to the metal oxide layer, wherein a first Gibbs freeenergy for the metal oxide layer is lower than a second Gibbs freeenergy for the PCMO layer, wherein the PCMO layer is characterized by afirst thickness and the metal oxide layer is characterized by a secondthickness, wherein the first thickness is twenty to fifty times morethan the second thickness.
 20. The electronic device of claim 19 thefirst metal layer comprises one of: aluminum, titanium, tantalum, gold,silver, or platinum.
 21. The electronic device of claim 19 wherein themetal oxide layer comprises one of: TiO₂, Ta₂O₅, NiO, WO₃, or Al₂O₃. 22.The electronic device of claim 19 wherein the second metal layercomprises one of: aluminum, titanium, tantalum, silver, copper, orplatinum.
 23. The electronic device of claim 19 wherein the PCMO layeris characterized by a first thickness, the first thickness being in therange of between 500 and 1000 angstroms.
 24. The electronic device ofclaim 19 wherein the PCMO layer is characterized by a first state havinga first resistance and a second state having a second resistance and themetal oxide layer is characterized by a third state having a thirdresistance state and a fourth state having a fourth resistance, andwherein the first resistance is higher than the second resistance andthe third resistance is higher than the fourth resistance.
 25. Theelectronic device of claim 24 wherein first resistance is similar invalue to the fourth resistance.